Metal-and-resin composite and method for making the same

ABSTRACT

A method for making a metal-and-resin composite, including: providing a metal substrate made of stainless steel; forming a plurality of nano pores on a surface of the metal substrate by chemical etching the metal substrate; forming an intermediate layer on the metal substrate by dipping the metal substrate in a coupling agent solution, the intermediate layer filling at least portion of each nano pore; and forming a resin member by placing the metal substrate in a mold and molding molten resin on a surface of the intermediate layer, the resin member covering and bonding with the intermediate layer, treating the metal substrate with a coupling solution having a silane compound coupling agent to make the intermediate layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Division Application of the U.S. patentapplication Ser. No. 14/610,154 filed on Jan. 30, 2015, the contents ofwhich are incorporated by reference herein.

FIELD

The present disclosure generally relates to a metal-and-resin compositeand a method for making the metal-and-resin composite.

BACKGROUND

Metal-and-resin composites are used in a wide range of industrial fieldsincluding the production of parts for automobiles, domestic appliances,industrial machinery, and the like. Generally, metal and resin arejoined together by an adhesive. However, this method cannot supply ahigh strength composite of metal and resin. There is a need to combinemetal and resin together.

BRIEF DESCRIPTION OF THE FIGURES

Implementations of the present technology will now be described, by wayof example only, with reference to the attached figures.

FIG. 1 is a cross-sectional view of an exemplary embodiment of ametal-and-resin composite.

FIG. 2 is a scanning electron microscope (SEM) image of a metalsubstrate having an intermediate layer.

FIG. 3 is a flow chart of a method for making a metal-and-resincomposite in accordance with an exemplary embodiment.

DETAILED DESCRIPTION

It will be appreciated that for simplicity and clarity of illustration,where appropriate, reference numerals have been repeated among thedifferent figures to indicate corresponding or analogous elements. Inaddition, numerous specific details are set forth in order to provide athorough understanding of the embodiments described herein. However, itwill be understood by those of ordinary skill in the art that theembodiments described herein can be practiced without these specificdetails. In other instances, methods, procedures and components have notbeen described in detail so as not to obscure the related relevantfeature being described. Also, the description is not to be consideredas limiting the scope of the embodiments described herein. The drawingsare not necessarily to scale and the proportions of certain parts may beexaggerated to better illustrate details and features of the presentdisclosure.

The term “comprising” when utilized, means “including, but notnecessarily limited to”; it specifically indicates open-ended inclusionor membership in the so-described combination, group, series and thelike.

FIG. 1 illustrates a metal-and-resin composite 100 according to anexemplary embodiment. The composite 100 includes a metal substrate 10,an intermediate layer 30 formed on the metal substrate 10, and a resinmember 50 covering the intermediate layer 30, to bond with the metalsubstrate 10.

The metal substrate 10 can be made of stainless steel, aluminum alloy,titanium alloy, aluminum-magnesium alloy, or zinc alloy. The metalsubstrate 10 has a plurality of nano pores 11 through a chemical etchingprocess. The nano pores 11 have a diameter of about 10 nm to about 1000nm, and a depth of about 0.1 μm to about 20 μm.

The intermediate layer 30 comprises coupling agent. The coupling agentcan be a titanate coupling agent, a zirconate coupling agent, a silanecoupling agent, a boric acid ester coupling agent, or a sulfonic acidcoupling agent. The intermediate layer 30 fills at least a portion ofeach nano pore 11 and covers the metal substrate 10. The intermediatelayer 30 has a thickness of about 0.5 nm to about 10 nm. In at least oneexemplary embodiment, a portion of each nano pore 11 is unfilled withthe intermediate layer 30.

An energy dispersive spectroscopy (EDS) test indicates that surfaces ofthe intermediate layer 30 includes carbon having a mass percentage ofabout 2.58-2.87%, oxygen having a mass percentage of about 1.29-2.08%,silicon having a mass percentage of about 0.59-0.72%, chromium having amass percentage of about 17.78-18.08%, manganese having a masspercentage of about 0.66-0.75%, iron having a mass percentage of about67.73-69.23%, and nickel having a mass of about 7.79-7.88%.

A scanning electron microscope (SEM) test indicates that theintermediate layer 30 covers the metal substrate 10, and fills at leastportion of each nano pore 11, a portion of each nano pore 11 is unfilledwith the intermediate layer 30. The portion of each nano pore 11unfilled with the intermediate layer 30 has a diameter of about 10 nm toabout 990 nm.

The resin member 50 can cover and bond with the intermediate layer 30,and fill the portion of each nano pore 11 unfilled with the intermediatelayer 30, such to bond with the metal substrate 10.

The resin member 50 can be made of polybutylene terephthalate (PBT),polyphenylene sulfide (PPS), polyethylene terephthalate (PET),polyetheretherketone (PEEK), polycarbonate (PC), or polyvinyl chloride(PVC). The bond between the resin member 50 and the intermediate layer30 includes chemical bonds, such that the resin member 50 can bond withthe metal substrate 10 through the chemical bonds. The tensile strengthof the composite 100 is about 10 KgF/cm² to about 100 KgF/cm², and theshear strength of the composite 100 is about 10 KgF/cm² to about 260KgF/cm².

Referring to FIG. 3, a flowchart is presented in accordance with anexample embodiment. The method 300 is provided by way of example, asthere are a variety of ways to carry out the method. The method 300described below can be carried out using the configurations illustratedin FIGS. 1-2, for example, and various elements of these figures arereferenced in explaining method 300. Each block shown in FIG. 3represents one or more processes, methods or subroutines, carried out inthe example method 300. Furthermore, the order of blocks is illustrativeonly and the order of the blocks can change according to the presentdisclosure. Additional blocks can be added or fewer blocks can beutilized, without departing from this disclosure. The example method 300can begin at block 301.

At block 301, a metal substrate 10 is provided. The metal substrate 10can be made of stainless steel, aluminum alloy, titanium alloy,aluminum-magnesium alloy, or zinc alloy.

At block 302, the metal substrate 10 is degreased by dipping the metalsubstrate 10 into a metal degreaser solution having a concentration ofabout 5-20 g/L. The dipping process can last for about 3 minutes toabout 10 minutes. The temperature of the degreaser solution can be about40° C. to about 75° C. In at least one exemplary embodiment, thedegreaser solution can be a conventional degreaser solution.

At block 303, the degreased metal substrate 10 is then etched through anacid treatment to remove a metal oxide film which may naturally form onthe metal substrate 10 when the metal substrate 10 is exposed to air.This acid treatment can be carried out by dipping the metal substrate 10in an acid solution for about 0.5 minutes to about 5 minutes. The acidsolution can have a temperature of about 50° C. to about 60° C., and aconcentration of about 5-20 g/L. The acid solution can be selected fromat least one of a group consisting of hydrochloric acid, phosphoricacid, sulphuric acid, nitric acid and hydrofluoric acid. It is to beunderstood that the metal substrate 10 has not been etched during theacid treatment. The metal substrate 10 is then cleaned to removeetch-resulting impurities.

At block 304, the metal substrate 10 is chemical etched to form aplurality of nano pores 11 on a surface of the metal substrate 10. Thechemical etching can be carried out by dipping the metal substrate 10into a chemical etching solution at a temperature of about 10° C. toabout 120° C. The chemical etching process can last for about 1 minuteto about 120 minutes. The chemical etching solution can be a sulphuricacid solution having a concentration of about 100-980 ml/L. The nanopores 11 have a diameter of about 10 nm to about 1000 nm, and a depth ofabout 0.1 μm to about 20 μm.

At block 305, an intermediate layer 30 is formed on the metal substrate10 and filled at least portion of each nano pore 11 through a surfacecoupling treatment. The intermediate layer 30 has a thickness of about0.5 nm to about 10 nm. The surface coupling treatment can be carried outby dipping the metal substrate 10 into a coupling solution at atemperature of about 25° C. to about 100° C. The surface couplingtreatment can last for 1 second to about 5 minutes. The couplingsolution can include solvent and coupling agent having a concentrationof about 10 ml/L to about 100 ml/L. The coupling agent can be a titanatecoupling agent, a zirconate coupling agent, a silane compound couplingagent, a boric acid ester coupling agent, or a sulfonic acid couplingagent. The solvent can be water or methanol. The intermediate layer 30has a thickness of about 0.5 nm to about 10 nm. In at least oneexemplary embodiment, a portion of each nano pore 11 is unfilled withthe intermediate layer 30.

At block 306, the metal substrate 10 is dried at a temperature of about25° C. to about 140° C. The metal substrate 10 can be dried naturally,or dried in an oven.

An energy dispersive spectroscopy (EDS) test indicates that a surface ofthe intermediate layer 30 formed in EXAMPLE 3 includes carbon having amass percentage of about 2.58-2.87%, oxygen having a mass percentage ofabout 1.29-2.08%, silicon having a mass percentage of about 0.59-0.72%,chromium having a mass percentage of about 17.78-18.08%, manganesehaving a mass percentage of about 0.66-0.75%, iron having a masspercentage of about 67.73-69.23%, and nickel having a mass of about7.79-7.88%.

A scanning electron microscope (SEM) test indicates that theintermediate layer 30 covers the metal substrate 10, and fills at leastportion of each nano pore 11, a portion of each nano pore 11 is unfilledwith the intermediate layer 30. The portion of each nano pore 11unfilled with the intermediate layer 30 has a diameter of about 10 nm toabout 990 nm.

At block 307, a resin member 50 is formed on the intermediate layer 30to bond with the metal substrate 10 through an injection process. Theinjection process can be carried out by placing the metal substrate 10into an injection mold (not shown), and molten resin is injected intothe mold, and covers and bonds a surface of the intermediate layer 30and fills the portion of each nano pore 11 unfilled with theintermediate layer 30, forming the resin member 50. The composite 100 isthus formed. During the injection process, the molten resin is kept at atemperature of about 220° C. to about 320° C. The resin member 40 can bemade of polybutylene terephthalate (PBT), polyphenylene sulfide (PPS),polyethylene terephthalate (PET), polyetheretherketone (PEEK),polycarbonate (PC), or polyvinyl chloride (PVC). The bond between theresin member 50 and the intermediate layer 30 includes chemicalbondings, such the resin member 50 can bond with the metal substrate 10through the chemical bondings. The tensile strength of the composite 100is about 10 KgF/cm² to about 100 KgF/cm², and the shear strength of thecomposite 100 is about 10 KgF/cm² to about 260 KgF/cm².

EXAMPLE 1

In this example, the metal substrate 10 was made of stainless steelSUS304, and the resin member 50 was made of PBT.

The metal substrate 10 was degreased by dipping in a degreaser solutionhaving a concentration of 20 g/L and a temperature of 75° C., allowingthe metal substrate 10 to be ultrasonically cleaned, for 5 min.

The degreased metal substrate 10 was etched by dipping in a hydrochloricacid solution having a concentration of 200 g/L and a temperature of 50°C., allowing the metal substrate 10 to be etched for 0.5 min.

The etched metal substrate 10 was chemical etched by dipping in asulphuric acid solution having a concentration of 300 ml/L and atemperature of 70° C., allowing the metal substrate 10 to be chemicaletched for 10 min.

The chemical etched metal substrate 10 was surface coupling treated bydipping in a coupling solution having a temperature of 25° C., allowingthe metal substrate 10 to be surface coupling treated for 10 seconds toform an intermediate layer 30 on the metal substrate 10. The couplingsolution includes methanol and zirconate coupling agent having aconcentration of 30 ml/L.

The metal substrate 10 was dried in an oven having an interiortemperature of 60° C. for 15 min.

Molten PBT resin having a temperature of 285° C. was injected to asurface of intermediate layer 30, and finally formed the resin member50.

EXAMPLE 2

In this example, the metal substrate 10 was made of stainless steelSUS306, and the resin member 50 was made of PPS.

The metal substrate 10 was degreased by dipping in a degreaser solutionhaving a concentration of 5 g/L and a temperature of 75° C., allowingthe metal substrate 10 to be ultrasonically cleaned, for 10 min.

The degreased metal substrate 10 was etched by dipping in a hydrochloricacid solution having a concentration of 200 g/L and a room temperature,allowing the metal substrate 10 to be etched for 5 min.

The etched metal substrate 10 was chemical etched by dipping in ahydrochloric acid solution having a concentration of 980 ml/L and atemperature of 120° C., allowing the metal substrate 10 to be chemicaletched for 10 min.

The chemical etched metal substrate 10 was surface coupling treated bydipping in a coupling solution having a temperature of 40° C., allowingthe metal substrate 10 to be surface coupling treated for 60 seconds toform an intermediate layer 30 on the metal substrate 10. The couplingsolution includes water and zirconate coupling agent having aconcentration of 20 ml/L.

The metal substrate 10 was dried in an oven having an interiortemperature of 60° C. for 15 min.

Molten PPS resin having a temperature of 320° C. was injected to asurface of intermediate layer 30, and finally formed the resin member50.

EXAMPLE 3

In this example, the metal substrate 10 was made of stainless steelSUS316, and the resin member 50 was made of PA.

The metal substrate 10 was degreased by dipping in a degreaser solutionhaving a concentration of 15 g/L and a temperature of 60° C., allowingthe metal substrate 10 to be ultrasonically cleaned, for 3 min.

The degreased metal substrate 10 was etched by dipping in a hydrochloricacid solution having a concentration of 150 g/L and a room temperature,allowing the metal substrate 10 to be etched for 3 min.

The etched metal substrate 10 was chemical etched by dipping in asulphuric acid solution having a concentration of 900 ml/L and atemperature of 10° C., allowing the metal substrate 10 to be chemicaletched for 120 min.

The chemical etched metal substrate 10 was surface coupling treated bydipping in a coupling solution having a temperature of 25° C., allowingthe metal substrate 10 to be surface coupling treated for 15 seconds toform an intermediate layer 30 on the metal substrate 10. The couplingsolution includes water and silane coupling agent having a concentrationof 30 ml/L.

The metal substrate 10 was dried in an oven having an interiortemperature of 120° C. for 5 min.

Molten PA resin having a temperature of 220° C. was injected to asurface of intermediate layer 30, and finally formed the resin member50.

It is to be understood, however, that even through numerouscharacteristics and advantages of the present disclosure have been setforth in the foregoing description, together with details of assemblyand function, the disclosure is illustrative only, and changes may bemade in detail, especially in the matters of shape, size, andarrangement of parts within the principles of the disclosure to the fullextent indicated by the broad general meaning of the terms in which theappended claims are expressed.

What is claimed is:
 1. A method for making a metal-and-resin composite,comprising: providing a metal substrate, the metal substrate being madeof stainless steel; forming a plurality of nano pores on a surface ofthe metal substrate by chemical etching the metal substrate; forming anintermediate layer on the metal substrate by dipping the metal substratein a coupling agent solution, the intermediate layer filling at leastportion of each of the nano pores; forming a resin member placing themetal substrate in a mold and molding molten resin on a surface of theintermediate layer, the resin member covering and bonding with theintermediate layer; and treating the metal substrate with a couplingsolution having a silane compound coupling agent to make theintermediate layer.
 2. The method as claimed in claim 1, the method offorming the intermediate layer comprises dipping the metal substrate inthe coupling agent solution having a concentration of approximately 10ml/L to approximately 100 ml/L and a temperature of approximately 25° C.to approximately 100° C. for approximately 1 second to approximately 5minutes, a thickness of the intermediate layer is in a range ofapproximately 0.5 nm to approximately 10 nm.
 3. The method as claimed inclaim 1, wherein the coupling agent is a titanate coupling agent, azirconate coupling agent, the silane compound coupling agent, a boricacid ester coupling agent, or a sulfonic acid coupling agent.
 4. Themethod as claimed in claim 1, the method of forming the nano porescomprises dipping the metal substrate in a chemical etching solutionhaving a concentration of approximately 100-980 ml/L and a temperatureof approximately 10° C. to approximately 120° C. for approximately 1minute to approximately 120 minutes, and then drying the coupling agentsolution to form the intermediate layer.
 5. The method as claimed inclaim 1, wherein diameters of the nano pores are in a range ofapproximately 10 nm to approximately 1000 nm, and depths of the nanopores are in a range of approximately 0.1 μm to of the nano pores are ina range of approximately 20 μm.
 6. The method as claimed in claim 1,wherein a portion of each of the nano pores is not filled with theintermediate layer, and a diameter of the portion of each of the nanopores not filled with the intermediate layer is in a range ofapproximately 10 nm to approximately 990 nm.
 7. The method as claimed inclaim 6, wherein the resin member fills the portion of each of the nanopores which are not filled with the intermediate layer.
 8. The method asclaimed in claim 1, wherein the resin member is made of polybutyleneterephthalate, polyphenylene sulfide, polyethylene terephthalate,polyetheretherketone, polycarbonate, or polyvinyl chloride.
 9. Themethod as claimed in claim 1, wherein the resin member and theintermediate layer are bonded primarily through chemical bonds.
 10. Amethod for making a metal-and-resin composite, comprising: providing ametal substrate; forming a plurality of nano pores on a surface of themetal substrate by chemical etching the metal substrate; forming anintermediate layer on the metal substrate by dipping the metal substratein a coupling agent solution, the intermediate layer filling at leastportion of each of the nano pores; and forming a resin member by placingthe metal substrate in a mold and molding molten resin on a surface ofthe intermediate layer, the resin member covering and bonding with theintermediate layer.
 11. The method as claimed in claim 10, the method offorming the intermediate layer comprises dipping the metal substrate inthe coupling agent solution having a concentration of approximately 10ml/L to approximately 100 ml/L and a temperature of approximately 20 oCto approximately 100 oC for approximately 1 second to approximately 5minutes, a thickness of the intermediate layer is in a range ofapproximately 0.5 nm to approximately 10 nm.
 12. The method as claimedin claim 10, wherein the coupling agent is a titanate coupling agent, azirconate coupling agent, a silane compound coupling agent, a boric acidester coupling agent, or a sulfonic acid coupling agent.
 13. The methodas claimed in claim 10, the method of forming the nano pores comprisesdipping the metal substrate in a chemical etching solution having aconcentration of about 100-980 ml/L and a temperature of approximately10 oC to approximately 120 oC for approximately 1 minute toapproximately 120 minutes, and then drying the coupling agent solutionto form the intermediate layer.
 14. The method as claimed in claim 10,wherein diameters of the nano pores are in a range of approximately 10nm to approximately 1000 nm, and depths of the nano pores are in a rangeof approximately 0.1 μm to of the nano pores are in a range ofapproximately 20 μm.
 15. The method as claimed in claim 10, wherein aportion of each of the nano pores is not filled with the intermediatelayer, and a diameter of the portion of each of the nano pores notfilled with the intermediate layer is in a range of approximately 10 nmto approximately 990 nm.
 16. The method as claimed in claim 15, whereinthe resin member fills the portion of each of the nano pores which arenot filled with the intermediate layer.
 17. The method as claimed inclaim 10, wherein the resin member is made of polybutyleneterephthalate, polyphenylene sulfide, polyethylene terephthalate,polyetheretherketone, polycarbonate, or polyvinyl chloride.
 18. Themethod as claimed in claim 10, wherein the resin member and theintermediate layer are bonded primarily through chemical bonds.
 19. Themethod as claimed in claim 10, wherein the metal substrate is made ofstainless steel, aluminum alloy, titanium alloy, aluminum-magnesiumalloy, or zinc alloy.